Sprayable adhesive for gypsy moth pheromone beads

ABSTRACT

An adhesive composition for a insect-control agent, such as gypsy moth pheromone beads, provides retention and water insolubility to such pesticide upon deposit of an aqueous mixture of such adhesive composition and insect-control agent. The adhesive composition concentrate comprises a salt such as sodium sulfate, an ethoxylated alkylphenol, a polymeric adhesive material, and a high molecular weight acrylate polymer.

This is a continuation of application Ser. No. 07/866,200, filed Apr.09, 1992, now abandoned.

TECHNICAL FIELD OF THE INVENTION

The present invention is in the technical field of compositionscontaining insect-control agents, mainly pheromone beads that can beapplied to foliage by spraying the composition, particularly when thespraying is conducted from an airplane.

BACKGROUND OF THE INVENTION

The North American strain of gypsy moths (species Lymantria dispar), orits ancestral European strain, has been known in North America since thelater 1800's, and by 1889 serious damage from this strain of gypsy mothwas being-reported in wooded areas by researchers. Gypsy moths areconsidered devastating insect pests in their larva stage when they areleaf-eating caterpillars. These caterpillars can ravage entire forests.As adults, the gypsy moths do not have working mouth parts, so theycannot feed, and they live only a few days or weeks. The North Americangypsy moths have wings, but cannot use them to fly. Instead they catch abreeze and glide on it. Thus the spread of this strain of gypsy moth isnot considered rapid, and researchers are able to wipe out centers ofinfestation when detected. Thus to an extent the North American strainof gypsy moth has been suppressed, but since it is found in forests inNew England, the Northeast, and the Mid-Atlantic states, and has alsobeen detected as far west as the Pacific Northwest, over the manydecades of efforts it clearly has not been eradicated.

In the early 1980's the Asian strain of gypsy moth was introduced toNorth America, apparently being transported aboard foreign trade vesselsthat docked in Seattle, in Portland, Oreg., and in Vancouver, BritishColumbia. The caterpillars of this strain have been observed using tinythreads of silk to become airborne, permitting them to be carried offlike kites, and thus the caterpillars themselves spread to acres offorests inland. The capability of this Asian strain to spread isbelieved intensified by the fact that the females have working wings.The females fly. Their spread is more rapid than the North Americanstrain and hence wiping out a center of infestation is a much moredifficult task. It is possible that the Asian strain has spreadthroughout most of the North American continent.

The Asian strain of gypsy moth is also more threatening than the NorthAmerican strain because of the caterpillars' eating habits. They aremore voracious eaters and they feast on more varieties of trees than theNorth American gypsy moth caterpillars. While preferring oak, they willfeed on almost any tree or shrub. Known hosts include alder, apple,basswood, birch, box elder, hawthorn, hazelnut, mountain ash, poplar,willow and witch hazel trees, rose bushes, and sumac plants.

The introduction of the Asian strain of gypsy moth is believed to beadding to the destruction of thousands of trees and is leading to theincreased use of insect-control agents. The watersheds in Washington,Oregon and British Columbia are in jeopardy of damage. The nationalforests of the United States are believed in jeopardy. North Americanagriculture may be threatened, and is already burdened with the costs ofsuppressing these strains of gypsy moths.

The term "insect-control agent" is defined as any chemical that canalter or destroy the normal life cycle of the insect in question.Chemicals which can fall into this category are insecticides, miticides,phermones, and the like.

One weapon being used to combat the gypsy moth problem is displarlure, asex pheromone, which is known to disrupt the procreation cycle of atleast the North American strain of gypsy moth. The pheromone has beenused to lure the males to insecticides or to physical traps. Such traps,however, provide too limited an area of protection when the plant lifeto be protected extends over vast areas, which at times can be millionsof acres.

For large scale protection, one currently used method is to incorporatesuch pheromone as beads into a composition that can be sprayed overacres of foliage and there become attached to leaves and tree limbs andstems and the like, so that a male gypsy moth, now being attracted tothe surrounding multiple sources of the pheromone, becomes distracted tothe point of procreation failure. The males cannot located females insuch environment.

Such large scale protection requires the pheromone beads to be welldistributed throughout the canopy of a forest or other foliage area tobe protected. Such distribution is best achieved by spraying a pheromonebead-containing composition from above, and therefore from an airplane.The pheromone bead-containing composition must have a viscosity that issufficiently low for spraying. The pheromone bead-containing compositionmust include an adhesive or sticker (discussed in more detail below)which adheres the pheromone beads to the foliage that comes into contactwith the composition. The pheromone bead-containing composition, assprayed, generally contains a high level of water, and thus the variouscomponents of such composition are typically diluted with water prior tospraying to achieve a sprayable mixture. Such dilution, when thecomposition is sprayed from an airplane, is routinely made in-flight,using a simple recirculating pump to admix the various components priorto spraying.

An adhesive or sticker formulation, to be suitable for use for largescale spraying from an airplane, thus must be readily dispersible withwater, so as to be thoroughly admixed with the water and the pheromonebeads using a simple recirculating pump. The adhesive or stickertherefore must not only have the desired adhesive properties, which arediscussed in more detail below, but also have the relatively lowviscosity required for rapid water dispersibility using only simpleadmixing means such as a recirculating pump.

To be suitable for spraying from an airplane, the pheromonebead-containing composition must predictably fall to the target area,and not drift with the wind. Thus the droplets formed upon spraying mustbe of sufficient size. To provide suitably sized droplets generallydrift control agents are used. Drift control agents are compositionsthat promote coalescence of fine droplets into larger droplets orstrands of droplets, for instance fine mists of from about 200 to about800 microliters or strands of several inches long, which size range isgenerally considered suitable to minimize the drifting of compositionswhen sprayed. A drift control agent for use in pheromone bead-containingcompositions, however, must also be readily water dispersible, and mustnot interfere with the performance of the adhesive or sticker. A typicaldrift control agent will interfere with the performance of a sticker andwill be difficult to disperse in water using a simple recirculating pumpor the like without the inclusion of a water miscible solvent of sometype in the drift control formulation. Such type of solvents, however,generally will add flash point characteristics to the formulation whichis not desirable.

As to the adhesive or sticker performance, as discussed more fillybelow, the adhesive should provide not merely good bonding between thepheromone beads and the foliage, but also bonding that is resistant toweather conditions, particularly rain and wind.

It is an object of the present invention to provide an adhesiveformulation that can be used with pheromone beads, dusts, flakes, powderand the like solid forms of this distracter, and other pesticides forwhich there are similar use techniques and performance goals. It is anobject of the present invention to provide such adhesive formulationthat provides excellent water insolubility characteristics to thedeposit film. It is an object of the present invention to provide suchan adhesive formulation that provides excellent retention of the activecomponents, such as the pheromone beads, on the foliage. It is an objectof the present invention to provide such an adhesive formulation that isreadily dispersible in water without any high energy admixing and thuscan be readily admixed with simple equipment such as a recirculatingpump. It is an object of the present invention to provide such anadhesive formulation that provides a pheromone bead-containingcomposition, or the like, that can be easily sprayed from an airplane,not only because of its water dispersibility, but also because of itsdrift properties. It is an object of the present invention to providesuch an adhesive formulation without the use of any flash point creatingsolvents. It is also an object of the present invention to providepheromone bead-containing compositions including such an adhesiveformulation, and a method for using such pheromone bead-containingformulation. These and other objections of the present invention aredescribed in more detail below.

DISCLOSURE OF THE INVENTION

The present invention provides an adhesive composition for aninsect-control agent, which adhesive composition provides retention andwater insolubility to the insect-control agent upon its deposit in anaqueous mixture onto foliage. Such adhesive composition is comprised of:

from about 0.01 to about 5.0 parts by weight of an inorganic salt, suchas sodium sulfate;

from 0 to about 0.03 parts by weight of an ethoxylated alkylphenol;

from about 1 to about 60 parts by weight of a polymeric adhesive solids;

from about 0.015 to about 1.5 parts by weight of an high molecularweight acrylate polymer solids as the salt form;

and water.

The present invention also provides a method for preparing such anadhesive composition, a sprayable mixture including such an adhesivecomposition, an insect-control agent and dilution water. The presentinvention also provides a method for distributing such an insect-controlagent by spraying. These and other embodiments of the invention aredescribed more fully below.

PREFERRED EMBODIMENTS OF THE INVENTION

The sprayable adhesive of the present invention may be considered afortified or combination adhesive. It may be used as, or as a substitutefor, stickers that are employed to increase the retention of sprays ordust deposits on plants by resisting the various factors involved inweather. Stickers used commercially may include proteinaceous materials,such as milk products, wheat flour, blood albumin and gelatin, oils,gums, resins and fine clays. Some commercially used stickers produceelastic films when deposited on leaves. Many stickers also possess somewetting and spreading characteristics, such as stickers that consist ofthe salts of sulfates or sulfated alcohols, esters of fatty acids, alkylsulfonates and petroleum sulfonates. Generally, a sticker is a substancewhich increases the firmness of attachment of finely-divided solids orother water-soluble materials to a surface. A sticker's performance ofmay be measured in terms of its resistance to time, wind, water,mechanical, and at times chemical, action.

Heretofore most commercially available stickers suffer from poor waterinsolubility, low retention properties, and/or ease of application,particularly when the most desired application method is spraying. These"deficiencies" of commercial stickers generally either arise fromattempts to employ such stickers for a demanding application, such asthe spray distribution of pheromone beads, or become more apparent whentried for such a use. In contrast, the present invention provides afortified adhesive that:

(1) Can be used with pheromone beads, dusts, flakes, powders and thelike solid forms of pheromone, and other insect-control agents for whichthere are similar use techniques and performance goals;

(2) Provides excellent water insolubility to the deposit film;

(3) Provides excellent retention of the pheromone beads and the like onthe host foliage;

(4) Is readily dispersible in water and thus is easily diluted withwater; and

(5) Can be sprayed from an airplane without drift problems.

The purpose of distributing pheromone beads is to provide a confusionsource, and for that purpose persistency of the bonding between thebeads and host foliage is highly desired. The pheromone beads are notconsumed in their intended performance. The distribution of pheromonebeads is not an application where, after placement, a slow release ofthe active component is desired. Thus certain characteristics of somecommercial stickers, such as slow degradation of the deposit film,render such stickers unsuitable for other than temporary persistency ofthe pheromone beads, while instead the greatest degree of persistency isdesired. The very optimum desired performance of a sticker for pheromonebeads is to provide a bond to the foliage for as long as a pheromonebead continues to act as a sex lure to the male gypsy moth, or as longas such host foliage survives. A slow release of the pheromone beadsover a time period of a few weeks or so is a deposit characteristic thatcounters the optimization of the use of pheromone beads.

A good performance of the adhesive properties of a pheromonebead-containing composition, upon deposit on foliage surfaces,particularly on leaf surfaces, requires preferably a retention of atleast about 50 or 60 percent of the pheromone beads at a low pheromonebeads to adhesive ratio, despite adverse weather conditions, such asrain and high winds, and greater retention performance, for instance theretentions of 80 or 90 percent or more of the pheromone beads, is highlydesirable. A good performance of the adhesive properties of a pheromonebead-containing composition, upon deposit on foliage surfaces,particularly on leaf surfaces, requires preferably that the adhesive, asdeposited, provides water insolubility to the pheromone beads despitesevere rain conditions, for instance continuous rain in mounts of 4 or 5inches of rain. A good performance of the adhesive properties of apheromone bead-containing composition, upon deposit on foliage surfaces,particularly on leaf surfaces, requires preferably that the waterinsolubility properties of the deposits develop within only a short timeperiod, and survive for long time periods. A commercial scaledistribution of the pheromone beads should not be thwarted by rainfallsthat occur a couple of hours later, nor should the deposits unduly losethe desired water insolubility and find resistance during dry periods,regardless of whether such periods continue for weeks. Moreover, thepersistence desired of the deposits makes it preferable that the desiredretention and water insolubility properties, which provide the desiredresistance to rain and wind, continue without undue diminishment, for atleast 3 or 4 weeks, and preferably even longer time periods, after theinitial distribution. The combination adhesive of the present inventionmeets such performance standards, and at times surpasses them, at lowconcentrations of the formulation in the spray mixture, and hence lowpheromone beads to adhesive ratios.

Wide scale distribution of pheromone beads to the canopy of a forest orother foliage area in need of protection from gypsy moth infestation isrequired. Such wide scale distribution often necessitates the sprayingof the composition from an airplane, using only simple equipment, suchas a recirculating pump and the like, for admixing the adhesive with thedilution water and the pheromone beads, as discussed above. Anyformulation that is to be so diluted in-flight should have a viscosityof no more than about 2,000 cps Brookfield, and preferably it shouldhave viscosities that are lower than this ceiling. The variousembodiments of the adhesive formulation of the present inventionroutinely have viscosities within the range of from about 100 to about1000 cps Brookfield, and thus are well under the practical viscosityceiling. The various embodiments of the adhesive formulation of thepresent invention have been found to be readily dispersible in waterwithout the incorporation of any solvent that may provide flash pointcharacteristics to the formulation.

The adhesive formulation of the present invention further incorporates ahigh molecular weight polymer of the type that is used in drift controlagents, without any loss of the low-viscosity characteristics, and isbelieved to alone provide sufficient drift control without theincorporation into the spray mixture of any additional additives.

The advantageous use of the adhesive formulation of the presentinvention as the sole component to be admixed with the dilution waterand pheromone beads simplifies the formation of the diluted spraymixture, and is a preferred embodiment of the present invention.

In an embodiment, the present invention is an adhesive composition for ainsect-control agent, which adhesive composition provides retention andwater insolubility to the insect-control agent upon its deposit in anaqueous mixture onto foliage. Such adhesive composition is comprised of:

from about 0.01 to about 5.0 parts by weight of an inorganic salt suchas sodium sulfate;

from 0 to about 0.03 parts by weight of an ethoxylated alkylphenol;

from about 1 to about 60 parts by weight of a polymeric adhesive solids;

from about 0.015 to about 1.5 parts by weight of an high molecularweight acrylate polymer solids as the salt form;

and water. The ethoxylated alkylphenol is a C₆₋₁₀ alkyl phenoxyethoxyethanol, wherein the alkyl may be linear or branched chained, andwherein the ethoxyethanol substituent has about 6 or more ethoxy units,and has an HLB of at least 10. The polymeric adhesive is a polyacrylatemultipolymer mixture or a polyurethane dispersion. The high molecularweight acrylate polymer has an intrinsic viscosity of at least about 18,a mole percent of acrylic acid mer units of from about 5 to about 50,and a mole percent of acrylamide mer units of from about 50 to about 95,the acrylic polymer being in the salt form. The amount of the water issufficient to provide the composition with a viscosity of no more than2,000 cps Brookfield. Such adhesive composition would also contain anyoil or surfactants or the like that are incorporated together with anyof the components as supplied, before the components are admixed to formthis adhesive composition. Such other materials are not believed to bein any way active components of the adhesive composition, and therefore,while their presence is not believed deleterious to the composition,such inadvertent materials are not enumerated above.

In preferred embodiments, as to this adhesive composition: the salt suchas sodium sulfate is present in the composition in an amount from about1.0 to about 2.25 parts by weight same basis; the ethoxylatedalkylphenol is present in the composition in an amount from about 0.001to about 0.02 parts by weight same basis; the polymeric adhesive ispresent in the composition in an amount from about 20 to about 50 partsby weight same basis; and/or the high molecular weight acrylate polymeris present in the composition in an amount from about 0.45 to about 1.1parts by weight same basis.

The adhesive composition in another preferred embodiment is acomposition comprised of:

from about 0.01 to about 5.0 percent of the inorganic salt such assodium sulfate;

from 0 to about 0.03 percent of the ethoxylated alkylphenol;

from about 1 to about 60 percent of the polymeric adhesive solids;

from about 0.015 to about 1.5 percent of the high molecular weightacrylate polymer solids as the salt form;

and the balance the water.

In another preferred embodiment the adhesive composition is acomposition comprised of:

from about 0.01 to about 5.0 percent of the inorganic salt such assodium sulfate;

from 0 to about 0.03 percent of the ethoxylated alkylphenol;

from about 1 to about 60 percent of the polymeric adhesive solids;

from about 0.015 to about 1.5 percent of the high molecular weightacrylate polymer solids as the salt form;

and the balance the water.

In another preferred embodiment the adhesive composition contains as thepolymeric adhesive is a polyacrylate multipolymer, described in moredetail below.

In further preferred embodiment, the high molecular weight acrylatepolymer is comprised of from about 20 to 40 mole percent of sodiumacrylate mer units and from about 60 to about 80 mole percent of theacrylamide met units.

The present invention, in another embodiment, is a method of preparingan adhesive composition for a insect-control agent that providesretention and water insolubility to the insect-control agent upondeposit of an aqueous mixture of the adhesive composition and theinsect-control agent on foliage, comprising admixing:

from about 0.01 to about 5.0 parts by weight of an inorganic salt suchas sodium sulfate;

from 0 to about 0.03 parts by weight of an ethoxylated alkylphenol;

from about 15 to about 75 parts by weight of an adhesive;

from about 0.5 to about 5 parts by weight of an acrylic polymer latex;

and water;

wherein the ethoxylated alkylphenol is a C₆₋₁₀ alkyl phenoxyethoxyethanol, wherein the alkyl may be linear or branched chained, andwherein the ethoxyethanol substituent has about 6 or more ethoxy units;

wherein the adhesive is a polyacrylate multipolymer mixture or apolyurethane dispersion containing from about 30 to about 65 weightpercent polymer solids;

wherein the acrylic polymer latex is a water-in-oil emulsion containingfrom about 20 to about 40 weight percent of an acrylic polymer aspolymer solids, the acrylic polymer having an intrinsic viscosity of atleast about 18, a mole percent of acrylic acid mer units of from about 5to about 50, and a mole percent of acrylamide mer units of from about 50to about 95, the acrylic polymer being in the salt form; and

wherein the amount of the water admixed is sufficient to provide thecomposition with a viscosity of no more than 2,000 cps Brookfield.

In a preferred embodiment, the method above more particularly comprisesadmixing:

from about 1.0 to about 2.25 parts by weight of the salt such as sodiumsulfate;

from 0.001 to about 0.02 parts by weight of the ethoxylated alkylphenol;

from about 20 to about 50 parts by weight of the adhesive;

from about 1.5 to about 3.5 parts by weight of the acrylic polymerlatex;

and 55 to 75 parts by weight water;

wherein the admixing results in an adhesive composition containing atotal of about 100 parts by weight.

In another embodiment, the present invention provides a sprayableaqueous mixture for distributing a insect-control agent that providesretention and water insolubility to the insect-control agent upondeposit of an aqueous mixture of the adhesive composition and theinsect-control agent on foliage, comprising:

from about 0.01 to about 5.0 parts by weight of an inorganic salt suchas sodium sulfate;

from 0 to about 0.03 parts by weight of an ethoxylated alkylphenol;

from about 1 to about 60 parts by weight of a polymeric adhesive solids;

from about 0.015 to about 1.5 parts by weight of an high molecularweight acrylate polymer solids as the salt form;

from about 20 to about 50 parts by weight of the insect-control agent;and

from about 40 to about 80 parts by weight water;

wherein the ethoxylated alkylphenol is a C₆₋₁₀ alkyl phenoxyethoxyethanol, wherein the alkyl may be linear or branched chained, andwherein the ethoxyethanol substituent has about 6 or more ethoxy units;

wherein the polymeric adhesive is a polyacrylate multipolymer mixture ora polyurethane dispersion;

wherein the high molecular weight acrylate polymer has an intrinsicviscosity of at least about 18, a mole percent of acrylic acid mer unitsof from about 5 to about 50, and a mole percent of acrylamide mer unitsof from about 50 to about 95, the acrylic polymer being in the saltform; and

wherein the amount of the water is sufficient to provide the mixturewith a viscosity of no more than 2,000 cps Brookfield.

In preferred embodiments, the above described mixture contains pheromonebeads as the insect-control agent and has a viscosity of no more than1,000 cps Brookfield.

The present invention in another embodiment is a method of distributingan insect-control agent comprising spraying a mixture a described aboveonto foliage. In preferred embodiment the spraying is conductedin-flight from an airplane. In another preferred embodiment theinsect-control agent that is sprayed is pheromone beads.

The Test Procedure

The following laboratory test procedure measures the retention of.deposits of pheromone beads from droplets on plant foliage and theresistance of such deposits to various weather conditions, namely rain,strong wind, and variations in time elapse between application and rainor heavy wind conditions. The retention by resistance to rain aspect ofthe test is also a determination of the water insolubility of thedeposits. In all instances the pheromone beads used arc commerciallyavailable pheromone beads under the tradenames Agri 129 bead or RaccmioDisparlure bead, both from AgriSense Company of Fresno, Calif.Formulations containing an adhesive are prepared and diluted with waterand admixed with the pheromone beads to provide the test mixtures(defined in more detail below under "Standard Mixture"). Theconcentration of pheromone beads in the Standard Mixture is commensurateto that of mixtures as sprayed in commercial applications. One dropletof a given mixture is hand placed onto each of five leaves (northern redoak foliage). One droplet is approximately 500 microliters and containsabout 20 pheromone beads. The leaves arc then left lying at ambient roomtemperature and humidity for a predetermined drying period, after whichthey are exposed a water spray and/or mechanical agitation simulatingrespectively rainfall (in controlled and measured amount and rate) andwind (in standard degree and time duration). The number of pheromonebeads on each leaf is counted after the drying period and again afterexposure to simulated rain and/or wind, with the assistance of astandard dissecting microscope. The retention of the pheromone beads isreported as "Percent Recovery", that is: ##EQU1## Unless otherwisestated, the Percent Recovery reported herein for a given test is theaverage of the five replicates (five leaves). A Percent Recovery that isgreater than 100 percent is typically the result of small beads beinghidden from view when initially counted, which are exposed by theweather treatment.

As seen from the description above, the Test Procedure is a simulatedlaboratory procedure wherein retention and water insolubility ismeasured. As noted elsewhere herein, it is desirable that a sprayablemixture for pheromone beads and the like also have drift controlperformance. Such drift control performance can generally, however, bedetermined without actually spraying a diluted mixture, and the mixturesprepared for the Examples below are believed to have a sufficient degreeof drift control, and hence require no other additives for this purpose.

The Standard Mixture

The Standard Mixture for the various Examples, the Control and theComparative Examples below is as follows:

    ______________________________________                                        37        parts by weight                                                                           pheromone beads                                         63-(a + b + c)                                                                          parts by weight                                                                           soft water                                              a         parts by weight                                                                           commercial drift control agent,                                               when used                                               b         parts by weight                                                                           a commercial sticker,                                                         when used                                               c         parts by weight                                                                           the Combination Adhesive                                100       parts by weight                                                                           concentrate for the                                                           Standard Mixture                                        ______________________________________                                    

which concentrate is then diluted as needed with water to provide aStandard Mixture containing about 20 pheromone beads per 500microliters.

The Commercial Drift Control Agent

In all instances, there is no commercial drift control agent except thatused in the Control described below. That commercial drift controlproduct is comprised of a high molecular weight polymer havingvisco-elastic properties, held in the water phase of a water-in-oillatex, surfactants, a sulfonate and a water miscible organic solvent,and has a Brookfield viscosity before product dilution of about 1800cps.

The Commercial Sticker

Two different commercial stickers were used in either the "Control"formulation or in the Comparative Examples. These commercial stickersare designated herein as S-1 and S-2, and can be described generally asadhesive types of materials known for use in pheromone bead applicationformulations. The S-1 sticker is a carboxylated styrene butadiene resintype of adhesive.

The Control

The Control in all instances it is used in the following Examples is acombination of the S-1 commercial sticker and the drift control agent.In terms of the Standard Mixture formulation given above, the Controlcontains 20 parts by volume of the commercial drift control product,which contains about 1 percent actives, and the concentration "b" ofcommercial sticker in the Control's Standard Formulation ("b") is 3parts by weight per hundred parts by weight of sprayable mixture.

The Combination Adhesive

The Combination Adhesive is a formulation within the present invention,and its composition, as conveniently supplied for dilution with water,and of course addition of the pheromone beads, is as follows:

    ______________________________________                                                        General Weight                                                                            Preferred Weight                                  Component       Percentage  Percentage                                        ______________________________________                                        Soft Water      balance     55 to 75%                                         Sodium sulfate  0.01 to 5.0%                                                                               1.0 to 2.25%                                     Ethoxylated alkylphenol                                                                         0 to 0.03%                                                                              0.001 to 0.02%                                    Adhesive Emulsion                                                                             15 to 75%   20 to 50%                                         Acrylate Polymer Emulsion                                                                     0.5 to 5%   1.5 to 3.5%                                       ______________________________________                                    

Unless indicated otherwise, the Combination Adhesive as used in thefollowing Examples is as shown above wherein all weight percentages ofall the components are with the "preferred weight percentage" ranges. Itis used alone, without any commercial sticker or commercial driftcontrol product. The Adhesive Emulsion is preferably comprised of apolyacrylate multipolymer mixture or a polyurethane composition, ormixtures thereof, supplied in latex form. Such latices have a solidscontent of from about 1 to about 60, for the purpose of employing thegeneral and preferred percentages therefor given above. The AcrylatePolymer Emulsion is a water-in-oil ("w/o" or oil external) emulsion morefully described below. The ethoxylated alkyl phenol is a C₆₋₁₀ alkylphenoxy ethoxyethanol, wherein the alkyl may have a linear or branchedchain and the ethoxyethanol substituent may contain about 6 or moreethoxy units (--CH₂ CH₂ O--), and preferably have an HLB of 10 or above.Such ethoxylated alkyl phenols are well known nonionic surfactantscommercially available under the tradenames of Triton X, Igepal,Polytergent and others.

The Acrylate Polymer Emulsion

The Acrylate Polymer Emulsion, as set forth for the Combination Adhesivedescribed above, more specifically is comprised of a high molecularweight polymer having an Intrinsic Viscosity ("IV") of greater thanabout 18 or 20, and the polymer actives comprise from about 28 to 32weight percent of this Emulsion. The polymer is comprised of from about15 to about 35 mole percent sodium acrylate met units and from about 65to about 85 mole percent acrylamide met units.

The Combination Adhesives used in the following Examples haveviscosities, prior to dilution and addition of the pheromone beads offrom about 100 to about 700 cps Brookfield, and thus such CombinationAdhesives are easily dispersed in the dilution water.

The high molecular weight acrylate polymer is of the same type as usedin the above described commercial drift control product, but again thecombination, or fortified, adhesive composition of the present inventiondoes not contain any flash point creating solvent.

The various Combination Adhesive formulations used in the followingExamples are designated C-1, C-2, C-3, C-4, and C- 5. Of these, C-1 andC-5 contain a polyurethane type of adhesive, and the others contain amultipolymer polyacrylate type of adhesive.

Typical polyurethane dispersions arc those available under the tradenameof Bayhydrol, from Miles, Inc. These polyurethane dispersions have fromabout 35 to about 40 weight percent solids and exhibit a viscosity ofless than about 1000 cps. One such product which has been foundparticularly useful is Bayhydrol 121.

Typical polyacrylate multipolymers arc mixtures of (meth)acrylate estersof C₆₋₁₀ alcoh including an hydroxy-substituted ester such as2-hydroxyethyl acrylate, butyl acrylate, and methyl methacrylate, toprovide a somewhat flexible, but nontacky, adhesive, together with apolymer promoting water insolubility, such as a styrene-methacrylic acidcopolymer. Typical polyacrylate multipolymers arc commercially availableunder the UCAR tradename from Union Carbide. These products contain fromabout 40 to about 60 weight percent polymer solids and have viscositiesof less than about 100 cps. One such product preferred for use in thepresent invention is the UCAR-100 latex.

EXAMPLES 1 to 8

Standard mixtures were prepared containing from 3 to 13 weight percentof combination adhesives C-1 and C-2 described above. The Test Proceduredescribed above was employed to determine the Percent Recoveryperformances of such standard mixtures in resisting the equivalent of 5inches of rain after a two-hour drying period, and also after a 24-hourdrying period for the higher concentration standard mixtures. The testresults, including identification of the standard mixture concentration,the duration of the drying period, and the respective combinationadhesive used are set forth below in Table 1, together with theperformance test results for the Control under the same set ofparameters.

                  TABLE 1                                                         ______________________________________                                        Five Inches Rain Weather Condition                                                                           Drying                                         Example                                                                              Combination                                                                              Concentration "c"                                                                          Period                                                                              Percent                                  No.    Adhesive   (weight percent)                                                                           (hours)                                                                             Recovery                                 ______________________________________                                        1      C-1         3           2     116%                                     2      C-1         6           2     125%                                     3      C-1        13           2     102%                                     4      C-1        13           24    113%                                     5      C-2         3           2      46%                                     6      C-2         6           2     100%                                     7      C-2        13           2     104%                                     8      C-2        13           24     95%                                     Control                                                                              none       --           2      4%                                      Control                                                                              none       --           2      11%                                     Control                                                                              none       --           2      29%                                     Control                                                                              none       --           24     28%                                     ______________________________________                                    

EXAMPLES 9 to 12 and COMPARATIVE EXAMPLES A and B

Standard mixtures were prepared containing either 13 or 25 weightpercent of Combination Adhesives C-1, C-3, C4 and C-5 described above,and for comparison two standard mixtures were prepared using commercialstickers. In Comparative Example A the commercial sticker is S-1, knownto be a carboxylated styrene butadiene resin. The composition of the S-2commercial sticker used in Comparative Example B is not known. The TestProcedure described above was employed to determine the Percent Recoveryperformances of such standard mixtures in the resistance of theequivalent of 0.5 and 1.0 inches of rain after a two hour drying period.The test results, including identifications of the standard mixtureconcentrations and the combination adhesive or commercial sticker used,are set forth below in Table 2.

                  TABLE 2                                                         ______________________________________                                        Two Hour Drying Time Condition                                                                                 Percent                                      Example or          Concentration                                                                              Recovery                                     Comparative                                                                            Combination                                                                              "c" or "b"   0.5"  1.0"                                   Example No.                                                                            Adhesive   (weight percent)                                                                           Rain  Rain                                   ______________________________________                                         9       C-3        13%          65%   65%                                    10       C-4        25%          88%   66%                                    11       C-5        13%          100%  98%                                    12       C-1        25%          112%  130%                                   A        *           13%*        97%   97%                                    B        **         **           29%   32%                                    ______________________________________                                         *13% of S1 commercial sticker                                                 **unknown concentration of S2 commercial sticker                         

EXAMPLES 13 to 16 and COMPARATIVE EXAMPLES C and D

Standard mixtures were prepared containing either 13 or 25 weightpercent of Combination Adhesives C-1, C-3, C-4 and C-5 described above,and for comparison two standard mixtures were prepared using commercialstickers. In Comparative Example C the commercial sticker was the sameS-1 as used in Comparative Example A and is known to be a carboxylatedstyrene butadiene resin. The composition of the commercial sticker usedin Comparative Example D was the same S-2 as used in Comparative ExampleB. The Test Procedure described above was employed to determine thePercent Recovery performance of such standard mixtures in the resistanceof the equivalent of 0.5 and 1.0 inches of rain after a five hour dryingperiod. The test results, including identifications of the standardmixture concentrations and the combination adhesive or commercialsticker used, are set forth below in Table 3.

                  TABLE 3                                                         ______________________________________                                        Five Hour Drying Time Condition                                                                                Percent                                      Example or          Concentration                                                                              Recovery                                     Comparative                                                                            Combination                                                                              "c" or "b"   0.5"  1.0"                                   Example No.                                                                            Adhesive   (weight percent)                                                                           Rain  Rain                                   ______________________________________                                        13       C-3        13%          131%  115%                                   14       C-4        25%          100%  100%                                   15       C-5        13%           80%   70%                                   16       C-1        25%           93%  100%                                   C        *           13%*        108%  114%                                   D        **         **           114%  121%                                   ______________________________________                                         *13% S1 commercial sticker                                                    **S2 commercial sticker                                                  

EXAMPLES 17 and 18

Two standard mixtures were prepared using 13 weight percent of theCombination Adhesives designated C-1 and C-2 respectively, and the TestProcedure described above was used to determine the drying time periodrequired for development of water insolubility and rain resistance. Thedrying time periods varied from 30 to 360 minutes and the rain conditionemployed was the severe 5 inches of rain simulation. The Controlstandard mixture, described above, was also put through the same seriesof tests. The test results versus the drying times are set forth belowin Table 4. Example 17 uses C-1 adhesive; Example 18 uses C-2.

                  TABLE 4                                                         ______________________________________                                        Five Inches Rain Condition/13 Percent Combination Adhesive                           Percent Recovery Drying Time Period                                             30              90          240                                      Example No.                                                                            Min.   60 Min.  Min. 120 Min.                                                                             Min. 360 Min.                            ______________________________________                                        Control  1       9       14   24     38   43                                  17       2      33       107  106    90   88                                  18       7      36       95   95     94   97                                  ______________________________________                                    

EXAMPLES 19 to 24

Six standard mixtures were prepared using from 3 to 10 weight percent ofthe Combination Adhesives designated C-1 and C-2 respectively, and theTest Procedure described above was used to determine, for a 2 hourdrying time period, the water insolubility and rain resistanceproperties of these standard mixtures. The rain conditions employedvaried from a mild 1 inch to the severe 5 inches of rain simulation. TheControl standard mixture, described above, was also put through the sameseries of tests. The test results versus the inches of rain are setforth below in Table 5. Examples 19 to 21 use the C-1 adhesive; Examples22 to 24 use the C-2 adhesive.

                  TABLE 5                                                         ______________________________________                                        Two Hour Drying Time Condition                                                               Percent Recovery                                                              Inches of Rain                                                 Example                                                                              Concentration "c"                                                                           1      2            5                                    No.    (percent by weight)                                                                         Inch   Inches                                                                              3 Inches                                                                             Inches                               ______________________________________                                        Control                                                                              --             12    11    11      9                                   19     3%             41    32    33     23                                   20     6%            104    100   93     88                                   21     10%           113    110   106    85                                   22     3%            130    120   124    93                                   23     6%             98    85    93     86                                   24     10%           111    95    109    92                                   ______________________________________                                    

EXAMPLES 25 and 26

Two standard mixtures were prepared using 10 weight percent of theCombination Adhesives designated C-1 and C-2 respectively, and the TestProcedure described above was used to determine the drying time periodrequired for development of water insolubility and rain resistance. Thedrying time periods varied from 30 to 360 minutes and the rain conditionemployed was the severe 5 inches of rain simulation, as was done inExamples 17 and 18 above. The Control standard mixture, described above,was also put through the same series of tests. The test results are setforth below in Table 6. Example 25 uses C-1 adhesive; Example 26 usesC-2.

                  TABLE 6                                                         ______________________________________                                        Five Inches Rain Condition/10 Percent Combination Adhesive                           Percent Recovery Drying Time Period                                             30              90          240                                      Example No.                                                                            Min.   60 Min.  Min. 120 Min.                                                                             Min. 360 Min.                            ______________________________________                                        Control  2      15        9   29     63   87                                  25       0      5        39   74     61   41                                  26       3      2        82   33     102  102                                 ______________________________________                                    

EXAMPLES 27 8and 28

Two standard mixtures were prepared using 6 weight percent of theCombination Adhesives designated C-1 and C-2 respectively, and the TestProcedure described above was used to determine the drying time periodrequired for development of water insolubility and rain resistance. Thedrying time periods varied from 30 to 120 minutes and the rain conditionemployed was the severe 5 inches of rain simulation, similar to thetests of Examples 17, 18, 26 and 27 above. The Control standard mixture,described above, was also put through the same series of tests. The testresults are set forth below in Table 7. Example 27 uses the C-1adhesive; Example 28 uses C-2.

                  TABLE 7                                                         ______________________________________                                        Five Inches Rain Condition/6 Percent Combination Adhesive                             Percent Recovery Drying Time Period                                   Example No.                                                                             30 Min.  60 Min.    90 Min.                                                                              120 Min.                                 ______________________________________                                        Control    0       26          9      7                                       27        47       36         82     102                                      28        15       58         53      56                                      ______________________________________                                    

EXAMPLES 29 to 34

Six standard mixtures were prepared using either 3 or 6 weight percentof the Combination Adhesives designated C-1, C-4 and C-2 respectively,and the Test Procedure described above was used to determine, for a 2hour drying time period, the water insolubility and rain resistanceproperties to the severe rain condition of 5 inches of rain simulation.The Control standard mixture, described above, was also put through the5 inches of rain test. The test results and the amount and type ofadhesive used are set forth below in Table 8.

                  TABLE 8                                                         ______________________________________                                        Two Hour Drying Time Condition                                                Example                                                                              Combination                                                                              Concentration "c"                                                                           Percent Recovery                              No.    Additive   (percent by weight)                                                                         5 Inches Rain                                 ______________________________________                                        Control                                                                              --         *              4                                            29     C-1        3%            116                                           30     C-1        6%            125                                           31     C-4        3%             15                                           32     C-4        6%             60                                           33     C-2        3%             46                                           34     C-2        65            100                                           ______________________________________                                    

EXAMPLES 35 to 46

Twelve standard mixtures were prepared using from 10 to 26 weightpercent of each of the Combination Adhesives designated C-1, C-5, C-4,and C-3, and the Test Procedure described above was used to determineboth the rain resistance and wind resistance properties of the depositsof these mixtures after a drying period of 19 days. Separate groups ofleaves were used for the rain resistance and the wind resistance tests.The identities of the Combination Adhesives, their concentrations, theamount of rain and the duration of the wind employed for the tests, andthe test results, are set forth below in Table 9.

                  TABLE 9                                                         ______________________________________                                        Drying Period of 19 Days                                                                                   Percent Percent                                         Combi-                Recovery                                                                              Recovery                                 Example                                                                              nation   Concentration "c"                                                                          5 Inches                                                                              Two Hours                                No.    Adhesive (Weight Percent)                                                                           Rain    Fan Wind                                 ______________________________________                                        Control                                                                              --       --           86      100                                      35     C-1      26           95      101                                      36     C-1      13           65      90                                       37     C-1      10           102     103                                      38     C-5      26           92      95                                       39     C-5      13           93      72                                       40     C-5      10           78      101                                      41     C-4      26           89      99                                       42     C-4      13           90      93                                       43     C-4      10           81      76                                       44     C-3      26           81      99                                       45     C-3      13           67      98                                       46     C-3      10           16      95                                       ______________________________________                                    

EXAMPLES 47 to 58

Twelve standard mixtures were prepared using from 10 to 26 weightpercent of each of the Combination Adhesives designated C-1, C-5, C-4,and C-3, and the Test Procedure described above was used to determineboth the rain resistance and wind resistance properties of the depositsof these mixtures after a drying period of 33 days. Separate groups ofleaves were used for the rain resistance and the wind resistance tests.The identities of the Combination Adhesives, their concentrations, theamount of rain and the duration of the wind employed for the tests, andthe test results, are set forth below in Table 10.

                  TABLE 10                                                        ______________________________________                                        Drying Period of 19 Days                                                                                   Percent Percent                                         Combi-                Recovery                                                                              Recovery                                 Example                                                                              nation   Concentration "c"                                                                          5 Inches                                                                              Two Hours                                No.    Adhesive (Weight Percent)                                                                           Rain    Fan Wind                                 ______________________________________                                        Control                                                                              --       --           95      99                                       47     C-1      26           99      101                                      48     C-1      13           98      101                                      49     C-1      10           100     101                                      50     C-5      26           82      99                                       51     C-5      13           69      97                                       52     C-5      10           47      97                                       53     C-4      26           91      94                                       54     C-4      13           89      96                                       55     C-4      10           90      86                                       56     C-3      26           89      97                                       57     C-3      13           58      100                                      58     C-3      26           47      84                                       ______________________________________                                    

The inorganic salt is including in the various compositions forviscosity control, and of the many inorganic salts available, it isbelieved that sodium salts are preferred, and while a sodium salt suchas sodium chloride could of course be employed, sodium sulfate providesmore ions per mole and is preferred for such viscosity control purpose.

The term "foliage" as used herein includes, but is not limited to,leaves.

Unless otherwise expressly stated herein, all percentages are weightpercentages.

Industrial Applicability of the Invention

The present invention is applicable to the forestry and agricultureindustries and any other industries employing insect-control agents.

I claim:
 1. A sprayable aqueous mixture for distributing ainsect-control agent that provides retention and water insolubility tosaid insect-control agent upon deposit of an aqueous mixture of saidadhesive composition and said insect-control agent on foliage,comprising:from about 0.01 to about 5.0 parts by weight of an inorganicsalt; from 0 to about 0.03 parts by weight of an ethoxylatedalkylphenol; from about 1 to about 60 parts by weight of a polymericadhesive solids; from about 0,015 to about 1.5 parts by weight of anhigh molecular weight acrylate polymer solids as the salt from; fromabout 20 to about 50 parts by weight of said insect-control agent; andfrom about 40 to about 80 parts by weight water; wherein saidethoxylated alkylphenol is a C₆₋₁₀ alkyl phenoxy ethoxyethanol, whereinsaid alkyl may be linear or branched chained, and wherein saidethoxyethanol substituent has at least about 6 ethoxy units; whereinsaid polymeric adhesive is a polyacrylate multipolymer mixture or apolyurethane dispersion; wherein said high molecular weight acrylatepolymer has an intrinsic viscosity of at least about 18, a mole percentof acrylic acid met units of from about 5 to about 50, and a molepercent of acrylamide met units of from about 50 to about 95, saidacrylic polymer being in the salt form; wherein the amount of said wateris sufficient to provide said mixture with a viscosity of no more than2,000 cps Brookfield; and wherein said insect-control agent is pheromonebeads.
 2. A sprayable aqueous mixture for distributing a insect-controlagent that provides retention and water insolubility to saidinsect-control agent upon deposit of an aqueous mixture of said adhesivecomposition and said adhesive composition and said insect-control agenton foliage, comprising:from about 0.01 to about 5.0 parts by weight ofan inorganic salt; from 0 to about 0.03 parts by weight of anethoxylated alkylphenol; from about 1 to about 60 parts by weight of apolymeric adhesive solids; from about 0.015 to about 1.5 parts by weightof an high molecular weight acrylate polymer solids as the salt from;from about 20 to about 50 parts by weight of said insect-control agent;and from about 40 to about 80 parts by weight water; wherein saidethoxylated alkylphenol is a C₆₋₁₀ alkyl phenoxy ethoxyethanol, whereinsaid alkyl may be linear or branched chained, and wherein saidethoxyethanol substituent has at least about 6 ethoxy units; whereinsaid polymeric adhesive is a polyacrylate multipolymer mixture or apolyurethane dispersion; wherein said high molecular weight acrylatepolymer has an intrinsic viscosity of at least about 18, a mole percentof acrylic acid mer units of from about 5 to about 50, and a molepercent of acrylamide mer units of from about 50 to about 95, saidacrylic polymer being in the salt form; and wherein the amount of saidwater is sufficient to provide said mixture with a viscosity of no morethan 1,000 cps Brookfield.
 3. A method of distributing a insect-controlagent comprising:spraying the mixture of claim 1 onto foliage.
 4. Themethod of claim 3 wherein said spraying is conducted in-flight from anairplane.
 5. The method of claim 3 wherein said insect-control agent ispheromone beads.